CA2025707A1 - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- CA2025707A1 CA2025707A1 CA002025707A CA2025707A CA2025707A1 CA 2025707 A1 CA2025707 A1 CA 2025707A1 CA 002025707 A CA002025707 A CA 002025707A CA 2025707 A CA2025707 A CA 2025707A CA 2025707 A1 CA2025707 A1 CA 2025707A1
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- Prior art keywords
- epoxy resin
- group
- parts
- composition
- resin composition
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/549—Silicon-containing compounds containing silicon in a ring
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
EPOXY RESIN COMPOSITION
ABSTRACT
A water resistant epoxy resin composition is disclosed, said composition comprising an epoxy resin, a compound having at least two phenolic hydroxyl groups sufficient to cure the epoxy resin component, an aromatic nitrogen-containing silane coupling agent and an inorganic filler. The epoxy resin composition is well suited for use as a sealant for electronic components.
ABSTRACT
A water resistant epoxy resin composition is disclosed, said composition comprising an epoxy resin, a compound having at least two phenolic hydroxyl groups sufficient to cure the epoxy resin component, an aromatic nitrogen-containing silane coupling agent and an inorganic filler. The epoxy resin composition is well suited for use as a sealant for electronic components.
Description
- 2!~2~7~7 EPO~Y RESIN COMPOSITION
The present invention relates to an epoxy resin composition, and, more particularly, relates to an epoxy resin material which has an excellent moisture resistance and is highly qualified as a sealant for electronic components.
The last few years have witnessed rapid expansion in the electronic device and equipment sector, and this has resulted in the prodltction o large n~lmbers o semicond~ctor-based electronic components. Within the arena of epoxy resins used to seal semiconductors, there has also been an accompanying strong demand for technical improvements in correspondence to the required maintenance of the characteristics and properties of semiconductors. Among these, improvements in the moisture resistance of epoxy resins are particularly important.
With regard to the development of epoxy resins in response to this demand, epoxy resin compositions are known in which an epoxy group-containing silane, amino group-containing silane, mercapto group-containing silane, ureide group-containing silane, or phenol group-containing silane has been blended into epoxy resin (for example, refer to Japanese Patent Application Laid Open [Kokai~ Number 59-124923 [124,923/84]).
Nevertheless, the moisture resistance of these epoxy resin compositions is still inadequate, and, inter alia, they suffer from a sharp decline in bending strength after a boiling test in water. They are therefore unsatisfactory as sealants for electronic components.
2Q~5~7 As the result of extensive research, the present inventors discovered that the admixture o a special silane coupling agent into epoxy resin largely solves the preceding problem~ and the present invention was achieved based on this.
In other words, the present invention takes as its object the introduction of a strongly moisture-resistant epoxy resin composition which is highly qualified for use as a sealant for electronic components. The invention therefore relates to a composition comprising:
(A) 100 parts by weight of an epoxy resin having at least two epoxy groups in each molecule;
(B) a sufficient quantity of a compound having at least two phenolic hydroxyl groups in each molecule to cure component (A);
(C) from 0.05 to 70 parts by weight of a silane coupling agent selected from the group consisting of compounds represented by the formulas R3-x R3 (i) (RlO)XSi(CH2)y N Ar O Q and ( Rl O ) z s i ( C~l7~Ar ( O Q ) n 2~2~7~
wherein Rl and R2 are monovalent hydrocarbon groups having 1 to 6 carbon atoms, R3 is selected from the group consisting of the hydrogen atom and a monovalent hydrocarbon group having 1 to 6 carbon atoms, Ar is an organic group selected from ~' ~ ~0~, or ~ N H
in which Q is selected from the group consisting o~
the hydrogen atom and a trialkylsilyl group represented by the formula -SiR~3, where R4 is an alkyl group having 1 to 6 carbon atoms, x is an integer between 1 and 3, y is an integer between 1 and 6, z is 1 or 2 and n is an integer between zero and 2; and (D) from about 30 to about 6~0 parts by weight of an inorganic filler.
The present invention relates to a composition compos~d of (A) an epoxy resin, (B) a compound for curing component (A), (C) a silane coupling agent, described infra, and (D) an inorganic filler.
To explain this in greater detail, the epoxy resin comprising component (A) should be a compound which has at least 2 epoxy groups in its molecule and is cured by the compound having phenolic hydroxyl groups as discussed below for component (B), but its molecular structure and molecular weight are not specifically restricted. Epoxy resins within this context are exempli~ied by bisphenol-based aromatic epoxy resins, ~~ 2 ~ 2 ~
alicyclic epoxy resins based on, for example, cyclohexane derivatives, epoxy novolac-type epoxy resins, and halogen atom-containing (chlorine, bromine9 etc.) epoxy resins.
The component (B) used by the present invention functions as a curing agent in order to cure the aforementioned component (A), and it takes the form of a compound which has at least 2 phenolic hydroxyl groups in each molecule. Again, its molecular structure and molecular weight are not specifically restricted.
Examples of such compounds are phenol novolac-type phenolic resins and cresol novolac-type phenolic resin~.
This component should be used in quantities sufficient to bring about the curing of component (A)~ as readily determined by routine experimentation.
The silane coupling agent comprising component (C) is the component which distinguishes or characterizes the invention under consideration~ and it functions to bring about a remarkable improvement in the moisture resistance of the composition of the present invention.
Silane (C) is selected from the group consisting of compounds having formulas (i) and (ii):
(i) 1 ~ 1 .
(RlO)XSi(CH~)y N Ar O Q
(ii) (R O)zSi (C~12 ~ Ar(O Q)n 2~257~
In the above formulas, the groups Rl and R2 are independently selected monovalent hydrocarbon groups having 1 to 6 carbon atoms as exemplified by alkyl groups such as methyl, ethyl, propyl, and butyl; R3 is the hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, as exemplified by alkyl groups such as methyl, ethyl, propyl, and butyl, and aryl groups such as phenyl; the group Ar is an organic group selected from ~' ~' ~~, or ~ N H ~
and the group Q is the hydrogen atom or a trialkylsilyl group as represented by -SiR43 in which R4 is an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, and propyl. Furthermore, x is an integer having a value of 1 to 3, y is an integer having a value of 1 to 6, z is an integer having a value of 1 to 2, and n is an integer having a value of zero to 2.
The silane coupling agent under consideration is exemplifi~d by the following compounds.
H OSi (CH3)3 (H3C 0)3 Si (CH~)3 N ~S
fH3 OSi(CH3)3 (H3CO)3Si(CH~)3 N~S
f H3 ICH3 OH
(H5C20)2Si(CH2)3 N~S
2~7~7 H
(H3C )2Si(c 17)3 o Component (C) can be prepared, for e~ample, by a dehydrohalogenation reaction between (a) a triorganosilylalkyl halide and (b) an aminophenol, in the presence of (c) a hydrogen ha~ide binder. The triorganosilylalkyl halide may be represented by the following general ormula 'R2 13-~
(R O)XSi(CH2~yA
wherein Rl and R2 have their above defined meanings; the group A is a halogen atom selected from fluorine, chlorine, bromine or iodine; and x, y and z also have their above defined values.
The aminophenol ~b) may be represented by the general formula I
H - N Ar(O Q)p wherein Q, Ar and R3 have their above defined meanings and p is an inte~er having a value of 1 or 2.
The triorganosilylalkyl halide, or derivative thereof, comprising the component (a) used by this method is its principal starting material. Organosilicon compounds corresponding to this component (a) can be procured on an industrial basis. These organosilicon compounds are exemplified by gamma-chloropropyltri-methoxysilane and gan~a-chloropropylmethyldimethoxysilane.
~2~7 The aminophenol, or derivative thereof, comprising the component (b) used by this method participates in a dehydrohalogenation reaction with the aforesaid component (a) in the presence o~ a hydrogen halide binder to aford the silane coupling agent comprising component (C). Among such compounds, the following, for example, are available on an industrial basis: meta-aminophenol, ortho-aminophenol, para-aminophenol, and so forth.
When too little of silane (C) is added, no effects nssociated with its addition will appear, while the addition o too much will impair the native properties of the epoxy resin. Accordingly, it should be added at 0.05 to 70 weight parts, and preferably at 0.1 to 35 weight parts, per 100 weight parts component (A).
The inorganic filler (D) used by the present invention imparts such physical properties as cracking resistance, low stress, etc., to the composition of the present invention. This component takes the form of those fillers typically used in epoxy or silicone resins, and examples in this regard are silica, talc, mica, clay, glass fiber, etc. ~he component under consideration should be added at about 30 to about 600 weight parts and preferably at 200 to 450 weight parts per 100 weight parts component (A).
As necessary, various additives may also be suitably added and mixed into the epoxy resin composition o the present invention as long as the object of the present invention is not compromised, and examples here are release agents, such as natural and synthetic waxes and the metal salts of straight-chain ~atty acids; ~lame retardants, such as antimony trioxide; colorants such as carbon black; curing accelerators, such as imidazole and derivatives thereo~, tertiary amine derivatives, and 2~2~7 phosphine derivatives; stress-reducing agents, such as silicones; and so forth.
The epoxy resin composition of the present invention is quite aasily prepared by mixing the aforementioned components (A) through ~D) to homogeneity, or by mixing the aforementioned components (A) through (D) to homogeneity along with the various additives. In the case of use as a molding material~ the epoxy resin is preferably converted into a particulate by grinding or pulverizing to a suitable size.
The present invention is explained in greater detail below thro-tgh illustrative example~ in which parts = weight parts.
Example 1 Three hundred and fifty parts of fused silica (FB-74 from Denki Kagaku Kogyo Kabushiki Kaisha~ Japan) was placed in a Henschel mixer and preliminarily mixed for 15 minutes while spraying in 1.4 parts silane coupling agent as reported in Table 1. To this were then added 100 parts cresol novolac-type epoxy resin (EOCN-1020 from Nippon Kayaku Kabushiki Kaisha, Japan) 50 parts phenol novolac resin (BRG-557 from Showa Kobunshi Xabushiki Kaisha), l part carnauba wax (release agent), and 1.5 parts phenylphosphine (curing accelerator) followed by mixing and kneading for 4 to 6 minutes on a six-inch two-roll mill heated to 70 to 90 degrees Centigrade. Cooling then aforded the epoxy resin composition, which was pulverized to give the granular epoxy resin composition. The bending strength, water absorption, and bending strength after immersion in boiling water were measured on the obtained epoxy resin after curing and its fluidity when uncured was also measured. The obtained measurement values are reported 2~2~7~7 in Table 2. The following measurement methods were employed.
Measurement of the bendin~ stren~th~ water absorption~
and bendin~ stren~th after immersion in boilin~ water The epoxy resin composition was molded into a 90 x 10 x 4 (mm) test specimen under the following conditions using a transfer molder: molding temperature = 175 degrees Centigrade, molding pressure = 70 kg/cm2, and molding time - 2 minutes.
The obtained test specimen was post-cured or 9 hours at 170 degrees Centigradel and the bending strength and water absorption were measured on the post-cured test specimen in accordance with JIS K611-1979 (General Test Methods for Thermosetting Plastics).
With regard to testing after immersion in boiling water, a test specimen post-cured as above was introduced into a pressure cooker (2 atm, 120 degrees Centigrade), maintained there for 96 hours, removed, and its bending strength was then measured.
Measurement of the fluidity The spiral flow was measured based on SPI-EMMI
1-66~ and this value is reported for the fluidity.
~Q2-5~
Table 1 composition silane coupling agent number . . ~
(CH3)3SiO - NHCH7CH~CH~Si~OCH3~3 ( H3 ) 2 5\' ) 3~) (CH3)3SiO~NHCH2CH~CU~Si(OCH3)3 Tab1e 2 _ _ bending c trength (k~f/mm2) ¦ l compositioninitialafter immersion in water spiral number boiling water absorption flow (%) (inch) _ .
16.1 13.7 0.69 43 _ . _ _ _ __ 16.3 13.~ 0.70 42 _ _ 3 16.7 13.5 0.68 43 ~2~7~
Example 2 Epoxy resin compositions were prepared as in Example 1, but using the following silane coupling agent in the quantity of addition reported in Table 3 in place of the 1.4 parts silane coupling agent reported in Table 1 of Example 1.
(H3C)3SiO ~ M H C H7C H~C H~Si~O C H3)3 The bending strength nfter curing, bending strength after immersion in boiling water, water absorption, and fluidity were measured on these epoxy resin compositions as in Example 1, and these measurement results are reported in Table 4.
Table 3 , , , ., ~
composition numberuse quantity of silane coupling agent (parts) 4 0.5 . . . - .
1.0 _ ., 6 _ ~02~7~7 Table 4 bending strength (kgf/mm2) ~
compositioninitialafter immersion in water spiral number boiling water absorption flow (%) (inch) _ _ . _ 16.0 12.5 0.69 ~1 15.9 12.8 0.71 ~2 _ ~ _ .
15.7 ~3.0 0.71 ~2 Comparison Example Epoxy resin compositions were prepared proceeding as in Example 1, but using the silane coupling agents given below in Table 5 in place of the silane coupling agents given in Table 1 for Example 1. The properties of these compositions were measured as in Example 1, and the obtained results are reported in Table 6.
7 ~ ~
Table 5 _ composition silane coupling agent number _ _ _ _ 7 3-glycidoxypropyltrimethoxysilane _ 8 3-ureidopropyltrimethoxysilane C ~--C
[~ CH~
O --si L~ oCH3 )2 9 .
_ _ Table 6 bending ~ trength (kgf /mm2) composition initialafter immersion in water spiral number boiling water absorption flow (%) (inch) ., _ _ _ .
7 13.8 11.0 0.87 42 _ . ... . _~
8 13.2 11~5 0.67 43 . , .
9 12.7 9.6 0.71 ~8 . ... .. ...
.
The present invention relates to an epoxy resin composition, and, more particularly, relates to an epoxy resin material which has an excellent moisture resistance and is highly qualified as a sealant for electronic components.
The last few years have witnessed rapid expansion in the electronic device and equipment sector, and this has resulted in the prodltction o large n~lmbers o semicond~ctor-based electronic components. Within the arena of epoxy resins used to seal semiconductors, there has also been an accompanying strong demand for technical improvements in correspondence to the required maintenance of the characteristics and properties of semiconductors. Among these, improvements in the moisture resistance of epoxy resins are particularly important.
With regard to the development of epoxy resins in response to this demand, epoxy resin compositions are known in which an epoxy group-containing silane, amino group-containing silane, mercapto group-containing silane, ureide group-containing silane, or phenol group-containing silane has been blended into epoxy resin (for example, refer to Japanese Patent Application Laid Open [Kokai~ Number 59-124923 [124,923/84]).
Nevertheless, the moisture resistance of these epoxy resin compositions is still inadequate, and, inter alia, they suffer from a sharp decline in bending strength after a boiling test in water. They are therefore unsatisfactory as sealants for electronic components.
2Q~5~7 As the result of extensive research, the present inventors discovered that the admixture o a special silane coupling agent into epoxy resin largely solves the preceding problem~ and the present invention was achieved based on this.
In other words, the present invention takes as its object the introduction of a strongly moisture-resistant epoxy resin composition which is highly qualified for use as a sealant for electronic components. The invention therefore relates to a composition comprising:
(A) 100 parts by weight of an epoxy resin having at least two epoxy groups in each molecule;
(B) a sufficient quantity of a compound having at least two phenolic hydroxyl groups in each molecule to cure component (A);
(C) from 0.05 to 70 parts by weight of a silane coupling agent selected from the group consisting of compounds represented by the formulas R3-x R3 (i) (RlO)XSi(CH2)y N Ar O Q and ( Rl O ) z s i ( C~l7~Ar ( O Q ) n 2~2~7~
wherein Rl and R2 are monovalent hydrocarbon groups having 1 to 6 carbon atoms, R3 is selected from the group consisting of the hydrogen atom and a monovalent hydrocarbon group having 1 to 6 carbon atoms, Ar is an organic group selected from ~' ~ ~0~, or ~ N H
in which Q is selected from the group consisting o~
the hydrogen atom and a trialkylsilyl group represented by the formula -SiR~3, where R4 is an alkyl group having 1 to 6 carbon atoms, x is an integer between 1 and 3, y is an integer between 1 and 6, z is 1 or 2 and n is an integer between zero and 2; and (D) from about 30 to about 6~0 parts by weight of an inorganic filler.
The present invention relates to a composition compos~d of (A) an epoxy resin, (B) a compound for curing component (A), (C) a silane coupling agent, described infra, and (D) an inorganic filler.
To explain this in greater detail, the epoxy resin comprising component (A) should be a compound which has at least 2 epoxy groups in its molecule and is cured by the compound having phenolic hydroxyl groups as discussed below for component (B), but its molecular structure and molecular weight are not specifically restricted. Epoxy resins within this context are exempli~ied by bisphenol-based aromatic epoxy resins, ~~ 2 ~ 2 ~
alicyclic epoxy resins based on, for example, cyclohexane derivatives, epoxy novolac-type epoxy resins, and halogen atom-containing (chlorine, bromine9 etc.) epoxy resins.
The component (B) used by the present invention functions as a curing agent in order to cure the aforementioned component (A), and it takes the form of a compound which has at least 2 phenolic hydroxyl groups in each molecule. Again, its molecular structure and molecular weight are not specifically restricted.
Examples of such compounds are phenol novolac-type phenolic resins and cresol novolac-type phenolic resin~.
This component should be used in quantities sufficient to bring about the curing of component (A)~ as readily determined by routine experimentation.
The silane coupling agent comprising component (C) is the component which distinguishes or characterizes the invention under consideration~ and it functions to bring about a remarkable improvement in the moisture resistance of the composition of the present invention.
Silane (C) is selected from the group consisting of compounds having formulas (i) and (ii):
(i) 1 ~ 1 .
(RlO)XSi(CH~)y N Ar O Q
(ii) (R O)zSi (C~12 ~ Ar(O Q)n 2~257~
In the above formulas, the groups Rl and R2 are independently selected monovalent hydrocarbon groups having 1 to 6 carbon atoms as exemplified by alkyl groups such as methyl, ethyl, propyl, and butyl; R3 is the hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, as exemplified by alkyl groups such as methyl, ethyl, propyl, and butyl, and aryl groups such as phenyl; the group Ar is an organic group selected from ~' ~' ~~, or ~ N H ~
and the group Q is the hydrogen atom or a trialkylsilyl group as represented by -SiR43 in which R4 is an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, and propyl. Furthermore, x is an integer having a value of 1 to 3, y is an integer having a value of 1 to 6, z is an integer having a value of 1 to 2, and n is an integer having a value of zero to 2.
The silane coupling agent under consideration is exemplifi~d by the following compounds.
H OSi (CH3)3 (H3C 0)3 Si (CH~)3 N ~S
fH3 OSi(CH3)3 (H3CO)3Si(CH~)3 N~S
f H3 ICH3 OH
(H5C20)2Si(CH2)3 N~S
2~7~7 H
(H3C )2Si(c 17)3 o Component (C) can be prepared, for e~ample, by a dehydrohalogenation reaction between (a) a triorganosilylalkyl halide and (b) an aminophenol, in the presence of (c) a hydrogen ha~ide binder. The triorganosilylalkyl halide may be represented by the following general ormula 'R2 13-~
(R O)XSi(CH2~yA
wherein Rl and R2 have their above defined meanings; the group A is a halogen atom selected from fluorine, chlorine, bromine or iodine; and x, y and z also have their above defined values.
The aminophenol ~b) may be represented by the general formula I
H - N Ar(O Q)p wherein Q, Ar and R3 have their above defined meanings and p is an inte~er having a value of 1 or 2.
The triorganosilylalkyl halide, or derivative thereof, comprising the component (a) used by this method is its principal starting material. Organosilicon compounds corresponding to this component (a) can be procured on an industrial basis. These organosilicon compounds are exemplified by gamma-chloropropyltri-methoxysilane and gan~a-chloropropylmethyldimethoxysilane.
~2~7 The aminophenol, or derivative thereof, comprising the component (b) used by this method participates in a dehydrohalogenation reaction with the aforesaid component (a) in the presence o~ a hydrogen halide binder to aford the silane coupling agent comprising component (C). Among such compounds, the following, for example, are available on an industrial basis: meta-aminophenol, ortho-aminophenol, para-aminophenol, and so forth.
When too little of silane (C) is added, no effects nssociated with its addition will appear, while the addition o too much will impair the native properties of the epoxy resin. Accordingly, it should be added at 0.05 to 70 weight parts, and preferably at 0.1 to 35 weight parts, per 100 weight parts component (A).
The inorganic filler (D) used by the present invention imparts such physical properties as cracking resistance, low stress, etc., to the composition of the present invention. This component takes the form of those fillers typically used in epoxy or silicone resins, and examples in this regard are silica, talc, mica, clay, glass fiber, etc. ~he component under consideration should be added at about 30 to about 600 weight parts and preferably at 200 to 450 weight parts per 100 weight parts component (A).
As necessary, various additives may also be suitably added and mixed into the epoxy resin composition o the present invention as long as the object of the present invention is not compromised, and examples here are release agents, such as natural and synthetic waxes and the metal salts of straight-chain ~atty acids; ~lame retardants, such as antimony trioxide; colorants such as carbon black; curing accelerators, such as imidazole and derivatives thereo~, tertiary amine derivatives, and 2~2~7 phosphine derivatives; stress-reducing agents, such as silicones; and so forth.
The epoxy resin composition of the present invention is quite aasily prepared by mixing the aforementioned components (A) through ~D) to homogeneity, or by mixing the aforementioned components (A) through (D) to homogeneity along with the various additives. In the case of use as a molding material~ the epoxy resin is preferably converted into a particulate by grinding or pulverizing to a suitable size.
The present invention is explained in greater detail below thro-tgh illustrative example~ in which parts = weight parts.
Example 1 Three hundred and fifty parts of fused silica (FB-74 from Denki Kagaku Kogyo Kabushiki Kaisha~ Japan) was placed in a Henschel mixer and preliminarily mixed for 15 minutes while spraying in 1.4 parts silane coupling agent as reported in Table 1. To this were then added 100 parts cresol novolac-type epoxy resin (EOCN-1020 from Nippon Kayaku Kabushiki Kaisha, Japan) 50 parts phenol novolac resin (BRG-557 from Showa Kobunshi Xabushiki Kaisha), l part carnauba wax (release agent), and 1.5 parts phenylphosphine (curing accelerator) followed by mixing and kneading for 4 to 6 minutes on a six-inch two-roll mill heated to 70 to 90 degrees Centigrade. Cooling then aforded the epoxy resin composition, which was pulverized to give the granular epoxy resin composition. The bending strength, water absorption, and bending strength after immersion in boiling water were measured on the obtained epoxy resin after curing and its fluidity when uncured was also measured. The obtained measurement values are reported 2~2~7~7 in Table 2. The following measurement methods were employed.
Measurement of the bendin~ stren~th~ water absorption~
and bendin~ stren~th after immersion in boilin~ water The epoxy resin composition was molded into a 90 x 10 x 4 (mm) test specimen under the following conditions using a transfer molder: molding temperature = 175 degrees Centigrade, molding pressure = 70 kg/cm2, and molding time - 2 minutes.
The obtained test specimen was post-cured or 9 hours at 170 degrees Centigradel and the bending strength and water absorption were measured on the post-cured test specimen in accordance with JIS K611-1979 (General Test Methods for Thermosetting Plastics).
With regard to testing after immersion in boiling water, a test specimen post-cured as above was introduced into a pressure cooker (2 atm, 120 degrees Centigrade), maintained there for 96 hours, removed, and its bending strength was then measured.
Measurement of the fluidity The spiral flow was measured based on SPI-EMMI
1-66~ and this value is reported for the fluidity.
~Q2-5~
Table 1 composition silane coupling agent number . . ~
(CH3)3SiO - NHCH7CH~CH~Si~OCH3~3 ( H3 ) 2 5\' ) 3~) (CH3)3SiO~NHCH2CH~CU~Si(OCH3)3 Tab1e 2 _ _ bending c trength (k~f/mm2) ¦ l compositioninitialafter immersion in water spiral number boiling water absorption flow (%) (inch) _ .
16.1 13.7 0.69 43 _ . _ _ _ __ 16.3 13.~ 0.70 42 _ _ 3 16.7 13.5 0.68 43 ~2~7~
Example 2 Epoxy resin compositions were prepared as in Example 1, but using the following silane coupling agent in the quantity of addition reported in Table 3 in place of the 1.4 parts silane coupling agent reported in Table 1 of Example 1.
(H3C)3SiO ~ M H C H7C H~C H~Si~O C H3)3 The bending strength nfter curing, bending strength after immersion in boiling water, water absorption, and fluidity were measured on these epoxy resin compositions as in Example 1, and these measurement results are reported in Table 4.
Table 3 , , , ., ~
composition numberuse quantity of silane coupling agent (parts) 4 0.5 . . . - .
1.0 _ ., 6 _ ~02~7~7 Table 4 bending strength (kgf/mm2) ~
compositioninitialafter immersion in water spiral number boiling water absorption flow (%) (inch) _ _ . _ 16.0 12.5 0.69 ~1 15.9 12.8 0.71 ~2 _ ~ _ .
15.7 ~3.0 0.71 ~2 Comparison Example Epoxy resin compositions were prepared proceeding as in Example 1, but using the silane coupling agents given below in Table 5 in place of the silane coupling agents given in Table 1 for Example 1. The properties of these compositions were measured as in Example 1, and the obtained results are reported in Table 6.
7 ~ ~
Table 5 _ composition silane coupling agent number _ _ _ _ 7 3-glycidoxypropyltrimethoxysilane _ 8 3-ureidopropyltrimethoxysilane C ~--C
[~ CH~
O --si L~ oCH3 )2 9 .
_ _ Table 6 bending ~ trength (kgf /mm2) composition initialafter immersion in water spiral number boiling water absorption flow (%) (inch) ., _ _ _ .
7 13.8 11.0 0.87 42 _ . ... . _~
8 13.2 11~5 0.67 43 . , .
9 12.7 9.6 0.71 ~8 . ... .. ...
.
Claims (2)
1. A composition comprising:
(A) 100 parts by weight of an epoxy resin having at least two epoxy groups in each molecule;
(B) a sufficient quantity of a compound having at least two phenolic hydroxyl groups in each molecule to cure said epoxy resin (A);
(C) from 0.05 to 70 parts by weight of a silane coupling agent selected from the group consisting of compounds represented by the formulas (i) and (ii) wherein R1 and R2 are monovalent hydrocarbon groups having 1 to 6 carbon atoms, R3 is selected from the group consisting of the hydrogen atom and a monovalent hydrocarbon group having 1 to 6 carbon atoms, Ar is an organic group selected from the group consisting of and in which Q is selected from the group consisting of the hydrogen atom and a trialkylsilyl group represented by the formula -SiR43, where R4 is an alkyl group having 1 to 6 carbon atoms, x is an integer between 1 and 3, y is an integer between 1 and 6, z is 1 or 2 and n is an integer between zero and 2; and (D) from about 30 to about 600 parts by weight of an inorganic filler.
(A) 100 parts by weight of an epoxy resin having at least two epoxy groups in each molecule;
(B) a sufficient quantity of a compound having at least two phenolic hydroxyl groups in each molecule to cure said epoxy resin (A);
(C) from 0.05 to 70 parts by weight of a silane coupling agent selected from the group consisting of compounds represented by the formulas (i) and (ii) wherein R1 and R2 are monovalent hydrocarbon groups having 1 to 6 carbon atoms, R3 is selected from the group consisting of the hydrogen atom and a monovalent hydrocarbon group having 1 to 6 carbon atoms, Ar is an organic group selected from the group consisting of and in which Q is selected from the group consisting of the hydrogen atom and a trialkylsilyl group represented by the formula -SiR43, where R4 is an alkyl group having 1 to 6 carbon atoms, x is an integer between 1 and 3, y is an integer between 1 and 6, z is 1 or 2 and n is an integer between zero and 2; and (D) from about 30 to about 600 parts by weight of an inorganic filler.
2. An article of manufacture prepared from the composition of claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1246203A JP2843612B2 (en) | 1989-09-21 | 1989-09-21 | Epoxy resin composition |
| JP246203/89 | 1989-09-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2025707A1 true CA2025707A1 (en) | 1991-03-22 |
Family
ID=17145051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002025707A Abandoned CA2025707A1 (en) | 1989-09-21 | 1990-09-19 | Epoxy resin composition |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5075357A (en) |
| EP (1) | EP0418888B1 (en) |
| JP (1) | JP2843612B2 (en) |
| CA (1) | CA2025707A1 (en) |
| DE (1) | DE69022340T2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR960012452B1 (en) * | 1989-02-20 | 1996-09-20 | 토레이 가부시키가이샤 | Semiconductor device-encapsulating epoxy resin composition |
| GB9019513D0 (en) * | 1990-09-06 | 1990-10-24 | Shell Int Research | Reinforced thermoplastic composites |
| US5413379A (en) * | 1993-09-16 | 1995-05-09 | Honda Giken Kogyo Kabushiki Kaisha | Knee bolster structure |
| JP3349963B2 (en) * | 1998-10-21 | 2002-11-25 | 日本電気株式会社 | Flame-retardant epoxy resin composition and semiconductor device using the same |
| JP2008305395A (en) * | 2008-05-15 | 2008-12-18 | Psa Corp Ltd | Magnetic sensor for automatic vehicle guidance system |
| JP2015182978A (en) * | 2014-03-25 | 2015-10-22 | 信越化学工業株式会社 | Organic silicon compound, adhesive composition, and article |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL232473A (en) * | 1957-10-21 | |||
| US4282136A (en) * | 1979-04-09 | 1981-08-04 | Hunt Earl R | Flame retardant epoxy molding compound method and encapsulated device |
| JPS59124923A (en) * | 1982-12-29 | 1984-07-19 | Shin Etsu Chem Co Ltd | Epoxy resin composition |
| US4929665A (en) * | 1987-01-20 | 1990-05-29 | Dainippon Ink And Chemicals, Inc. | Thermoplastic resin composition |
| JPH0791446B2 (en) * | 1987-03-31 | 1995-10-04 | 株式会社東芝 | Resin-sealed semiconductor device |
-
1989
- 1989-09-21 JP JP1246203A patent/JP2843612B2/en not_active Expired - Fee Related
-
1990
- 1990-09-17 US US07/583,903 patent/US5075357A/en not_active Expired - Fee Related
- 1990-09-19 CA CA002025707A patent/CA2025707A1/en not_active Abandoned
- 1990-09-20 DE DE69022340T patent/DE69022340T2/en not_active Expired - Fee Related
- 1990-09-20 EP EP90118120A patent/EP0418888B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03109417A (en) | 1991-05-09 |
| JP2843612B2 (en) | 1999-01-06 |
| EP0418888A2 (en) | 1991-03-27 |
| EP0418888B1 (en) | 1995-09-13 |
| DE69022340D1 (en) | 1995-10-19 |
| US5075357A (en) | 1991-12-24 |
| EP0418888A3 (en) | 1992-01-15 |
| DE69022340T2 (en) | 1996-03-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |